Photographic developer



Patented Nov. 33, 1945 PHOTOGBAPMC DEVELOP Frederic R. Bean, Rochester.N. Y., asslgnor to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application June 25, 1M2,

Serial No. 448,415 I is ens.

This invention relates to photographic developing solutions and moreparticularly to concentrated photographic developing solutions and drymixtures of chemicals suitable for dissolving in water to formphotographic developing solutions.

In making concentrated solutions of Photo graphic developing compounds,reagents such as polyhydric, alcohols, amino alcohols, and causticalkalis have been used singly or in combinations to act as solubilizingagents for the developer in the presence of sodium sulflte. When caustica1- kall is used the developing solutions tend to have poor keepingproperties, when amino alcohols are used the solutions may give fog andthepolyhydric alcohols are not especially good solvents for sodiumsulfite.

I have found a class of compounds useful in making developer solutions,especially composipreservatives and prevent formation of sludge duringdevelopment.

Compounds useful in developing solutions according to my invention arethe alkali metal salts of aminomethane sulfonates and of aminomethanesulilnates as, for example, the sodium salts 'of amine and the solutionis warmed at about 50- 60 C. for about 30 minutes. If desired, one moleof solid sodium formaldehyde-bisulfite may be caused to react with themonoethanolamine in a similar manner. The resulting product may beisolated and added to a photographic developing solution, or if desired,the photographic ingredients may be added to the above solution and madeup to the required volume by the addition of water.

In a similar manner di-(p-hydroxye'thyl) aminpmethane sulfonate may beprepared as follows: 420 grams of diethanolamine and 536 grams of sodiumformaldehyde bisulfite are placed in 300- 400 cc. of water and themixture is warmed at about 50-60 C. for 30 minutes and allowed tostand-overnight at room temperature. The reaction product may beisolatedfrom the resulting syrupy reaction mixture by the addition oforganfi-hydroxyethylaminomethane sulfonates, di-(,B

hydroxyethyl) aminomethane sulfonate, ethylenediamino-bis-methanesulionate, ,B-hydroxyethylaminodimethylmethane sulfonate,cyclohexylaminomethane sulfonate, morpholihomethane sulfonate,p-carboxyphenylaminomethane sulfonate and sulfinate,ethylenediamino-bis-methane sulfinate, ethylenediamino-bis-dimethylmethane sul- -finate, carboxymethylaminomethane sulionate,

lo solvents such as acetone, methyl alcohol, tertiary butyl alcohol,etc., which cause the reaction product to precipitate out as fine whitecrystals.

' Aminomethanesulfonates of ketones capable of reacting with sodiumbisulfite may be prepared in a manner analagous to those above-describedby the reaction of an amine with a ketone and sodium bisulflte or aketone-bisulflte compound, by heating for a suitable length of time.

The aminomethanesulfinate compounds of the invention may, ior instance,be prepared by reaction of an amino compound with aldehyde sulfoxalatessuch as formaldehyde sulfoxalate. A typical aminomethanesuli'inatecompound useful in my invention, that is,di-sodlum-p-carboxyphenylaminomethane sulflnate, may be preparedasi'ollows: 34.2 grams of p-aminobenzoic acid are added to 30-40 cc. ofwater containing 10 grams of sodium hydroxide. Thereafter, 38.5 grams oftones by reaction with sodium bisulflte and an A suitable method ofpreparation oi-the above compoundis as follows: '75 cc. of 40%formaldehyde are added to 150,-200 cc. of water and then 104 grams oisodium bisulflte are then added. I To this solution are added 61 gramsor monoethanolformaldehyde sulioxalate are added to the hot solution andthe mixture heated at 70 C. for 1-2 hours. After cooling the reactionproduct is precipitated from the syrupy mixture by the addition ofacetone.

Qther aminomethane sulilnates are prepared in a similar manner byreactionol other amino compounds with formaldehyde sulioxalate, or othersuliox'alates as, for example, prepared by the reduction of aminomethanesulionates.

A method 01 preparing a mixture-of aminomethane sulionate and anaminomethane sulflnate compound is given as follows: molecularproportions of formaldehyde and sodium hydrosulflte are caused to reactin aqueous solution, and thereafter, the product consisting of sodiumformaldehyde sulioxalate and sodiumformaldehyde bi-' sulflte is reactedwith an amine or amines to form The compounds of my invention may beused in developing solutions, especially concentrated developingsolutions, as shown in the following examples which are intended onlyfor illustration.

Example 1 Sodium-,8-hydroxyethylaminomethane sulfonate grams 81.5p-Methylamino-phenol sulfate do 5.0 Potassium thiocyanate do 1.0Potassium bromide do 0.5 Hydroquinone r do 1.0 Water I e 250 For usethis solution is made to the required volume with water.

Example 2 Di-sodium ethylenediamino-bis-methane sulfonate grams '73p-Methylamino-phenol sulfate do 5.0 Potassium thiocyanate do 1.0Potassium bromide do 0.5 Water to 250 Example 3 Water 385 Sodium sulfitegrams 18 Acetic acid (glacial) cc; 10 Sodium-p-hydroxyethylaminomethanesulfonate grams 531 p-Methylamino phenol sulfate do 25 Hydroquinone do 6Potassium bromide do 10 Sodium thiocyanate do 6 Glycerin or 200 Water toliter 1 Example 4 Sodium-B-hydroxyethylaminomethane sulfinate grams 322Hydroquinone d 90 Potassium bromide do 6.3 Water to liter 1 In a similarmanner'a mixture of aminomethane sulfonate and sulfinate areincorporated into a developer formula in the amount required to makeconcentrated developers or dry mixtures of chemicals for dissolving inwater.

Example 5 Di-(phydroxylethyl) aminomethane sulfonate grams; 110p-Methylamino-phenol sulfate do 5 Potassium thiocyanate do 1 Potassiumbromide do 0.5

advisable, especially from the standpoint of economy, to use as muchsodium sulfite in the con-' centrated developing solutions, as ispossible, and adding the compounds of the invention as solubilizers andto aid in the preservation of the so lutions.

One advantageous feature of the compounds when used in developingsolutions, resides in their a mixture of 'sulfonate and sulfinatecompounds.

solubility characteristics. The compounds, especially the hydroxy alkylderivatives, are considerably more soluble than sodium sulfite andaccordingly are especially suitable for use inconcentrated developingsolutions. The anti-sludge properties of a developer containingcompounds of my invention were demonstrated as follows: several rolls ofamateur film were developed in a developing solution of the followingcomposition:

IIJ'he same number of rolls of the same film were developed under thesame conditions in a second developing solution of composition shown inExample 1 with the result that whereas a continuously heavier sludgeformed in the first developer after development of a certain number ofrolls of film, the second developer was nearly asclear as at first afterdeveloping the same amount of film.

Asshown in Example 3, the pH of the developing solutions may beregulated by the addition of acid compounds such as meta-bisulfites,bisulfites, acid sodium acetate, acetic acid, etc., or basic compoundsuch as sodium metaborate and the like. Suitable solid acids and-basesmay also be added to the dry mixtures of chemicals of my invention. Ofcourse, the compounds of my invention also aid in the regulation of pH.

Other aminomethanesulfonates useful in developing solutions according tomy invention may be prepared from aldehydes such as crotonic aldehyde,acrolein, etc., and ketones such as acetone, acetonyl-acetone, etc., byreaction with bisulfites and amines employing suitable conditons of timeand temperature.

It is to be understood that the disclosure herein is by way of exampleand that I consider as included in my invention all modifications andequivalents falling within the scope of the appended claims.

What I claim is:

1. A photographic developing solution comprising a. developing agent anda compound selected from the group consisting of alkali salts ofaminomethane sulfonates and aminomethane sulfinates.

2. A photographic developing solution comprising a developing agent andan alkali metal salt of an aminomethane sulfonate.

3. A photographic developing solution comprising a developing agent, analkali metal salt of an aminomethane sulfonate. and sodium sulfite.

4. A photographic developing solution comprising a developing agent and,d-hydroxyethylaminomethane sulfonate.

5. A photographic developing solution comprising a developing agent anda sodium salt of ethylenediamino-bis-methane sulfonate.

6. A photographic developing solution comprising a, developing agent andan alkali metal salt of an aminomethane sulfinate.

7. A photographic developing solution comprising a developing agent andan alkali metal salt of an aminomethane sulfinate and sodium sulfite.

8. A photographic developing solution comprising a developing agent andan alkali metal salt of ,B-hydroxyethylaminomethane sulfinate.

9. A solid mixture of chemicals suitable for forming a, photographicdeveloping solution by dissolving in water comprising a developing agentand a compound selected from. the group consisting of alkali metal saltsof aminomethane sulfonates and aminomethane sulilnates.

10. A solid mixture of chemicals suitable for forming a photographicdeveloping solution "by dissolving in water comprising a developingagent and an alkali metal salt of an aminomethane sulfonate. I

11. A solid mixture of chemicals suitable for forming a photographicdeveloping solution by dissolving in water comprising a developing agentand an alkali metal salt of an aminomethane sulflnate.

12. A solid mixture of chemicals suitable for forming a photographicdeveloping solution by dissolving in water comprising a developing agent-metal salt of an aminomethane and an alkali metal salt ofp-hydroxyethylaminomethane sulfonate.

13. A photographic developing solution comprising a developing agent, analkali metal salt oi an aminomethane sulfonate, and an alkalisltioncomis A photographic developing prising a. developing agent, analkali metal salt of an aminomethane w Sultanate, and an alkali metalsalt of an aminomethane sulfinate, and so- 15. A solid mixture ofchemicals suitable for forming a photographic developing solution bydissolving in water comprisinga developing agent and an alkali metalsalt of, an aminomethane sulionate and an alkali metal salt of'anaminomethane sulflnate.

